Green dye.



NITED STATES PATENT OFFICE.

RENE BOIIN, OF MANNHEIM, GERMANY, ASSIGNOR TO THE BADISCHE ANILIN ANDSODA FABRIK, OF LUDWIGSHAFEN, GERMANY.

GREEN D-YE.

SPECIFICATION forming part of Letters Patent No, 647,370, dated April10, 1900.

Application filed November 14, 1899. Serial No. 736,972- (Speoimensd Toall whom, it may concern:

Be it known that I, RENE BOHN, doctor of philosophy, a citizen of theSwiss Republic, residing at Mannheim, in the Grand Duchy of Baden andEmpire of Germany, have invented new and useful Improvements in theManufacture of Green Coloring-Matters, of which the following is aspecification.

In the specifications of Patents Nos. 631,614 and 633,950, grantedAugust 22, 1899, and September 26, 1899, respectively, I have describedthe production of a new oxidation product and new reduction product,respectively, from the naphthazarin intermediate product. In the Germanpatent applications B. 24,633 and B. 24,649 of the 24th and 26th ofApril, 1899, respectively, it is described how the said reduction andoxidation products can be converted into the naphthazarin intermediateproduct in a pure and crystalline condition.

My present invention relates to the manufacture of new greencoloring-matters from the said intermediate product, preferably in thispure crystallized form. My new green coloring-matters are obtained bytreating the said intermediate product with an aromatic amin, with orwithout the use of acondensing agent or solvent. The coloring-mattersare first obtained in the form insoluble in water, but can bereadilysulfonated to soluble sulfoacids. These sulfoacids dyeunmordanted wool from the acidbath, giving beautiful green shades.

The following examples will serve to further illustrate my invention andthe manner in which it is carried into eifect and my new col'oring-matters obtained.

Example 1: Mix about ten parts of the naphthazarin intermediate producthereinbefore defined with two hundred parts of low the melt to coolslowly, when the new 001- oring matter usually separates out in the formof long indigo-blue needles. Collect and dry in the usual way. Thecoloring-matter sion is complete.

so obtained is insoluble in water. To convertit into its sulfoacid,mixabout ten parts of the dry coloring-matter thus obtained with about twohundred parts of concentrated sulfuric acid, (containing aboutninety-five per cent. of H 80 Heat the mixture to a temperature of 40 toCentigrade and maintain at this temperature for about twelve hours. Thenpour the reaction product into water and pre cipitate the sulfoacidformed with common salt and collect in the usual way. The product soobtained is a blue-black powder readily soluble in water, giving abrilliant bluishgreen solution. In the presence of caustic soda andsodium carbonate the aqueous solution is green and with concentratedsulfuric acid the product dissolves with a pure-blue solution.

Example 2: Mix together about ten parts of the naphthazarin intermediateproduct hereinbefore defined with about two hundred parts of glacialacetic acid and twenty parts of para-toluidin. Boil the mixture untilthe solution, which is at first blue-violet, becomes a beautifulblue-green color. Allow the melt to cool slowly and collect thecoloring-matter that separates out. The coloring-matter so obtained isinsoluble in water. It can be readily sulfonated as follows: Add aboutten parts of the product to about two hundred parts of fuming sulfuricacid, (containing about twelve per cent. free SO Keep the acid coldthatis, below 50 centigrade-while adding the coloring-matter. Allow themixture to stand for about one hour and then pour the reaction mass intoone thousand parts of water and precipitate the coloringmatter withcommon salt. The product thus obtained is a greenish powder readilysoluble in water, giving a bright-green color.

Example 3: Dissolve about ten parts of the naphthazarin intermediateproduct hereinbefore defined in about one hundred parts of anilin, andheat the mixture to 100 centi grade. Then add about forty parts ofanilin hydrochlorate to the solution. The "solution, which is at firstblue-black in color, turns green. In about half an hour the conver- Pourthe reaction product into dilute hydrochloric acid, filter, andrecrystallize the precipitate from alcohol or acetic acid, and anilin.

glacial acetic acid. The coloring-matter so obtained has the sameproperties as the insoluble product as obtained in Example 1.

In the foregoing examples the anilin or para-toluidin can be replaced byother aromatic aminssuch as, for instance, orthotoluidin, para phenylenediamin benzidin, and the likeand similar products are in each caseobtained.

In the present application for patent I desire to claim, generically,the new green coloring-matters which can be obtained, as here-.

inbefore described,from the naphthazarin intermediate product and thearomatic amins, whether in the form insoluble in water or in the form ofsoluble sulfoacids, and, specifically, -I desire to claim thatcoloring-matter which is obtained by the treatment of the naphthazarinintermediate product with anilin both in the unsulfonated and sulfonatedform.

The coloring-1n atters which I desire to claim generically arecharacterized by the following properties: In the unsulfonated conditionthey are insoluble in water and caustic-soda solution, soluble insulfuric acid, in glacial In the sulfonated form it is readily solublein water, giving green-colored solutions, soluble in causticsodasolution,and soluble in concentrated sulfuric acid. The specificcoloring-matter obtained by the use of anilin which I desire to claim isin the unsulfonated condition insoluble in caustic-soda andcarbonate-of-soda solution, insoluble in water, soluble in 0on centratedsulfuric acid,giving green-blue solutions, in anilin giving a pure-greensolution, and in glacial acetic acid giving greenish-blue solution.

Now What I claim is l. A new green coloring-matter which can be obtainedfrom the naphthazarin intermediate product and an aromatic amin'which inthe unsulfonated form are insoluble in water and acetic-acid solution,soluble in sulfuric acid, in glacial acetic acid and anilin and in thesulfonated form are readily soluble in water giving a green-coloredsolution, soluble in caustic-soda solution and soluble in concentratedsulfuric acid, all substantially as described.

2. A new green coloring-matter which can be obtained from thenaphthazarin intermediate product and anilin and in the unsulfonatedform is insoluble in water and in caustic-soda solution, soluble inconcentrated sulfuric acid giving a green-blue solution and in anilin apure-green solution and which in the sulfonated form is soluble in watergiving a brilliant bluish-green solution which turns green in thepresence of caustic soda and sodium-carbonate and soluble inconcentrated sulfuric acid giving a brilliant blue solution, allsubstantially as described.

In testimony whereof I have hereunto set my hand in the presence of twosubscribing witnesses.

RENE BOHN.

WVitnesses: OSCAR BALLY,

ERNEST F. EHRHARnr.

